The complexity of lignin and hemicellulose segmentation has been known since the middle of the ninetieth century. Studies confirmed that all lignin units in coniferous species and 47-66% of lignin moieties in deciduous species are bound to hemicelluloses or cellulose molecules in lignin-carbohydrate complexes (LCC). Different types and proportions of lignin and polysaccharides present in biomass lead to the formation of LCC with a great variety of compositions and structures. The nature and amount of LCC linkages and lignin substructures affect the efficiency of pulping, hydrolysis, and digestibility of biomass. This review paper discusses the structures, compositions, and properties of LCC present in biomass and in the products obtained via pretreating biomass. Methods for extracting, fractionating, and analyzing LCC of biomass, pulp, and spent pulping liquors are critically reviewed. The main perspectives and challenges associated with these technologies are extensively discussed. LCC could be extracted from biomass following varied methods, among which dimethyl sulfoxide or dioxane (Björkman's) and acetic acid (LCC-AcOH) processes are the most widely applied. The oxidation and methylation treatments of LCC materials elucidate the locations and frequency of binding sites of hemicelluloses to lignin. The two-dimensional nuclear magnetic resonance analysis allows the identification of the structure and the quantity of lignin-carbohydrate bonds involved in LCC. LCC application seems promising in medicine due to its high anti-HIV, anti-herpes, and anti-microbial activity. In addition, LCC was successfully employed as a precursor for the preparation of spherical biocarriers.
Keywords: Fractionation; Lignin–carbohydrate complex (LCC); Milled wood lignin; NMR; Sustainable chemicals.